EP1975692A1 - Anzeigeelement - Google Patents

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Publication number
EP1975692A1
EP1975692A1 EP06843065A EP06843065A EP1975692A1 EP 1975692 A1 EP1975692 A1 EP 1975692A1 EP 06843065 A EP06843065 A EP 06843065A EP 06843065 A EP06843065 A EP 06843065A EP 1975692 A1 EP1975692 A1 EP 1975692A1
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EP
European Patent Office
Prior art keywords
group
display element
silver
electrolyte
sch
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Application number
EP06843065A
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English (en)
French (fr)
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EP1975692A4 (de
Inventor
Noriyuki Kokeguchi
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP1975692A1 publication Critical patent/EP1975692A1/de
Publication of EP1975692A4 publication Critical patent/EP1975692A4/de
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1506—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
    • G09G3/00—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes
    • G09G3/20—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters
    • G09G3/34—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source
    • G09G3/38—Control arrangements or circuits, of interest only in connection with visual indicators other than cathode-ray tubes for presentation of an assembly of a number of characters, e.g. a page, by composing the assembly by combination of individual elements arranged in a matrix no fixed position being assigned to or needed to be assigned to the individual characters or partial characters by control of light from an independent source using electrochromic devices
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13356—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements
    • G02F1/133562—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements on the viewer side
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09G—ARRANGEMENTS OR CIRCUITS FOR CONTROL OF INDICATING DEVICES USING STATIC MEANS TO PRESENT VARIABLE INFORMATION
    • G09G2320/00—Control of display operating conditions
    • G09G2320/02—Improving the quality of display appearance
    • G09G2320/0242—Compensation of deficiencies in the appearance of colours

Definitions

  • the present invention relates to an electrochromic display element utilizing silver dissolution and deposition.
  • viewing means for such electronic information mainly employed are those of light emitting types such as conventional liquid crystal displays and CRTs or recent organic electroluminescence displays.
  • electronic information includes document information, it is required to watch any of the above viewing means for a relatively long period.
  • the above viewing means are human friendly. It is common knowledge that light emitting type displays result in problems such as eye fatigue due to flicker, inconvenient portability, limitations in reading posture, necessity to look at still images, or an increase in power consumption.
  • reflection type displays having memory function
  • a system employing polarizing plates such as a reflection type liquid crystal
  • polarizing plates such as a reflection type liquid crystal
  • polymer dispersion type liquid crystals require high voltage and the contrast of the resulting images is insufficient due to utilizing the difference in refractive indices between organic compounds.
  • polymer network type liquid crystals result in problems such as application of high voltage and requirement of complicated TFT circuitry to enhance memory capability.
  • display elements employing electrophoresis require high voltage of at least 10 V and tend to suffer insufficient durability due to aggregation of electrophoretic particles.
  • electrochromic display elements though being drivable at a low voltage of at most 3 V, result in insufficient color quality of black and common colors (namely yellow, magenta, cyan, blue, and red) and tend to result in problems such that, in order to secure memory capability, the display cell requires a complicated film structure such as vapor deposition film.
  • ED electrodeposition
  • a conventional ED system display element has problem in that whiteness of a white background is insufficient.
  • a method is considered which incorporates a large amount of titanium oxide in an electrolyte layer.
  • this results in the problem that the electrolyte layer is thick, resulting in elevation of driving voltage or in lowering of reaction rate.
  • a colorant is incorporated in an electrolyte layer in order to adjust the tone of the white background.
  • a high colorant content of the electrolyte layer influences on reactivity of the electrolyte, and results in deterioration with time of the electrolyte.
  • an ED system display element when on white display, a reflectance at 550 nm is from 45% to 60%, has the highest sensitivity to viewer eyes, and an ED system display element exhibits its performance most effectively without deterioration with time and markedly improves the white background, in which a color tone-adjusting layer adjusted for a reflectance at 550 nm to be in the above range is provided on the viewer side separately from the electrolyte.
  • the present invention can provide a display element with high display contrast, which can be driven at a low voltage in a simple member construction, and gives a white impression to a viewer while suppressing white reflectance.
  • the present inventor has made an intensive study. As a result, he has found that a display element which can be driven at a low voltage in a simple member construction, provides high display contrast, and gives a white impression to a viewer while suppressing white reflectance is realized, the display element comprising an electrolyte containing silver or a compound containing silver in its chemical structure between opposed electrodes to be driven so as to cause dissolution and precipitation of silver, wherein a color tone-adjusting layer, a transparent electrode and an electrolyte layer being provided in that order as viewed from a viewing direction of the element, and wherein when white is displayed, a reflectance at 550 nm of the display element without the color tone-adjusting layer is from 45% to 60%.
  • the present inventors have completed the invention.
  • the display element of the present invention is an ED system display element comprising an electrolyte containing silver or a compound containing silver in its chemical structure between opposed electrodes which are subjected to driving operation so as to cause dissolution and precipitation of silver.
  • a display element which can be driven at a low voltage in a simple member construction, provides high display contrast and gives a white impression to a viewer while suppressing white reflectance, is realized, the display element comprising a color tone-adjusting layer between a viewer and an electrode (a transparent electrode) provided on the viewer side.
  • silver or a compound containing silver in the chemical structure is a collective term of compounds such as silver oxide, silver sulfide, metallic silver, colloidal silver particles, silver halide, silver complexes, or silver ions.
  • Types of phase states such as a solid state, a solubilized state in liquid, or a gaseous state, as well as types of charged states such as neutral, anionic or cationic are not particularly limited.
  • Fig. 1 is a schematic cross-sectional view showing one example of the structure of the ED display element of the invention.
  • Electrode 1 which is provided closer to ED display section E, is a transparent electrode such as an ITO electrode, and the other electrode, Electrode 2 is a metal electrode such as a silver electrode. Electrolyte 3, containing silver or a compound containing silver in the chemical structure, is placed between Electrodes 1 and 2. When voltage having a positive or negative polarity is applied across the electrodes, reduction-oxidation reaction is carried out on Electrodes 1 and 2, and a black silver image state in a reduced state and a transparent silver state in an oxidized state are reversibly changed.
  • Color tone-adjusting layer 4 is further provided between a viewer and Electrode 1, one of the opposed electrodes, which is provided closer to ED display section E.
  • a colorant a dye, a pigment or an optical brightening agent
  • a display element which incorporates a colorant in an electrolyte, has problem in storage stability of an element. For example, when such a display element is allowed to stand at high temperature and high humidity for long term, the colorant decomposes, resulting in color tone variation, and in low color reproduction efficiency for its addition amount on account of existing white pigment.
  • an optical brightening agent in an electrolyte to improve white display.
  • a technique which provides a color tone-adjusting layer outside opposed electrodes, and gives a white impression to a viewer while suppressing reflectance of a display element part without the color tone-adjusting layer.
  • the constitution of the invention can suppress reflectance of the display element part, decrease an addition amount of white pigment, whereby the gap between opposed electrodes can be reduced, resulting in improvement of dissolution and in cost reduction of materials.
  • a constitution layer which contains for example, a colorant such as a dye or a pigment, or an optical brightening agent (also called a bluing agent) in a polymer binder or a polymer film.
  • a colorant such as a dye or a pigment
  • an optical brightening agent also called a bluing agent
  • the dye include dyes described in European Patent No. 549,489 ; dyes ExF2 to 6 described in JP-A No. 7-152129 ; dyes AI-1 to 11 described in JP-A No. 3-251840 , page 308; dyes described in JP-A No. 6-3770 ; compounds represented by general formulas (I), (II) and (III) described in JP-A No.
  • yellow pigments of the pigments include C.I. (Color Index) Direct Yellow 86, C.I. Acid Yellow 23, C.I. Acid Yellow 79, C.I. Pigment Yellow 74, C.I. Pigment Yellow 128, and compounds designated as C.I. Nos. Y-3, Y-167, Y-97, Y-74, Y-12, Y-14, Y-17, T-55, Y-83, Y-154, Y-95, Y-193, Y-83, Y-34, Y-128, Y-93, Y-110, Y-139, Y-199, Y-147, Y-109, Y-13, Y-151, and Y-154.
  • C.I. (Color Index) Direct Yellow 86 C.I. Acid Yellow 23, C.I. Acid Yellow 79, C.I. Pigment Yellow 74, C.I. Pigment Yellow 128, and compounds designated as C.I. Nos. Y-3, Y-167, Y-
  • magenta pigments include Acid 52, C.I. Projet Mazenta, C.I. Pigment Red 122, and compounds designated as C.I. Nos. R-48:1, R-53:1, R-49:1, R-48:3, R-48:2, R-57:1, R-63:1, R-58:4, O-16, R-112, R-3, R-170, R-5, R-146, R-81, V-19, R-122, R-257, R-254, R-202, R-211, R-213, R-268, R-177, R-17, R-23 and R-31.
  • Preferred examples of cyan pigments include C.I. Acid Blue 9, C.I. Direct Blue 199, C.I.
  • the color tone-adjusting layer may be formed, coating a color tone-adjusting layer directly on a substrate or laminating on a substrate a film with a color tone-adjusting layer separately formed.
  • Colorants used in the invention are preferably colorants exhibiting blue color (blue colorants), and more preferably those having a wavelength giving absorption maximum, ⁇ max of from 600 to 700 nm.
  • a coating method is preferred in the invention which adds the colorants to a coating solution for a color tone-adjusting layer in an amount of from 0.01 to 10% by weight, disperses the coating solution in a known disperser to obtain a dispersion, and coats on a substrate the dispersion.
  • a binder in which the colorants are dispersed is preferably a hydrophilic binder such as polyvinyl alcohol or gelatin.
  • the colorants may be incorporated in a substrate constituting electrodes as a color tone-adjusting layer.
  • optical brightening agent examples include compounds of stilbene type, pyrazoline type, oxazole type, cumarin type, imidazole type, di-styryl-biphenyl type, thiazole type, triazole type, oxadiazole type, thiadiazole type, naphthoimide type, benzimidazole type, benzoxazole type, benzothiazole type, acenaphthene type, and diaminostilbene type.
  • Compounds of stilbene type are preferably used.
  • optical brightening agents of bis(benzoxazolyl)stilbene type optical brightening agents of bis(benzoxazolyl)naphthalene type, optical brightening agents of bis(benzoxazolyl)thiophene type, optical brightening agents of pyrazoline type, and optical brightening agents of cumarin type.
  • Preferred examples thereof include compounds of formula (I) through (V) described in JP-A 9-203984 , and as typical examples thereof, compounds I-(1) through I-(14), compounds II-(1) through II-(11), compounds III-(1) through III-(9), compounds IV-(1) through IV-(8), and compounds V-(1) through V-(5) described in JP-A 9-203984 are preferably employed.
  • the content ratio (by weight) of the optical brightening agent to the resin is usually from 0.01 to 40%, and preferably from 0.03 to 5%.
  • a reflectance at 550 nm of the display element without the color tone-adjusting layer is from 45% to 60%.
  • the reflectance can be controlled by adjusting the refractive index or addition amount of white scattering material contained in an electrolyte.
  • the white scattering material is titanium oxide
  • the coating amount thereof is preferably from 8 to around 30 g/m 2 .
  • the coating amount of titanium oxide exceeds 30 g/m 2 , the maximum reflectance is saturated, which is disadvantageous in reduction of space between opposed electrodes, which is required from viewpoints of resolution.
  • the coating amount of titanium oxide is less than 8 g/m 2 , the reflectance is too low, which cannot be compensated by a color tone-adjusting layer.
  • the reflectance can be measured employing a spectro-colorimeter CM-3700d, produced by Konica Minolta Sensing, Inc.
  • the electrolyte contains at least one of compounds represented by Formulas (1) and (2) and at least one of compounds represented by Formulas (3) and (4).
  • L represents an oxygen atom or CH 2
  • R 1 through R 4 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group, or an alkoxy group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group.
  • aryl group examples include a phenyl group and a naphthyl group.
  • cycloalkyl group examples include a cyclopentyl group and a cyclohexyl group.
  • alkoxyalkyl group examples include a ⁇ -methoxymethyl group, a ⁇ -methoxypropyl group.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group and a dodecyloxy group.
  • R 5 and R 6 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxyalkyl group or an alkoxy group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group
  • examples of the aryl group include a phenyl group, and a naphthyl group
  • examples of the cycloalkyl stoup include a cyclopentyl group, and a cyclohexyl group.
  • alkoxyalkyl group examples include a ⁇ -methoxymethyl group, a ⁇ -methoxypropyl group, while examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, and a dodecyloxy group.
  • the compounds represented by Formulas (1) and (2) in the invention are one type of electrolyte solvents.
  • Another solvent may be employed in combination in the display element of the present invention, as long as the purpose and effects of the present invention are not jeopardized.
  • tetramethylurea sulfolane, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, 2-(N-methyl)-2-pyrrolidinone, hexamethylphosphortriamide, N-methylpropionamide, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide, N-methylformamide, butyronitrile, propionitrile, acetonitrile, acetylacetone, 4-methyl-2-pentanone, 2-butanol, 1-butanol, 2-propanol, 1-propanol, ethanol, methanol, acetic anhydride, ethyl acetate, ethyl propionate, dim
  • solvents in the present invention may be the compounds described in J. A. Riddick, W. B. Bunger, T. K. Sakano, "Organic Solvents", 4th ed., John Wiley & Sons (1986 ), Y. Marcus, “Ion Solvation”, John Wiley & Sons (1985 ), C. Reichardt, "Solvents and Solvent Effects in Chemistry", 2nd ed., VCH (1988 ), G. J. Janz, R. P. T. Tomkins, “Nonaqueous Electrolytes Handbook", Vol. 1, Academic Press (1972 ).
  • the electrolyte solvent may be a single variety or a solvent mixture. However preferred is a solvent mixture containing ethylene carbonate. The added amount of ethylene carbonate is preferably from 10 to 90% by weight with respect to the total electrolyte solvent weight.
  • the specifically preferred electrolyte solvent is the solvent mixture of propylene carbonate/ethylene carbonate at a weight ratio of 7/3 to 3/7. When the ratio of propylene carbonate is more than 7/3, the response rate is lowered due to degradation of ionic conductivity, while when it is less than 3/7, the electrolyte tends to precipitate at low temperature.
  • R 7 and R 8 each represent a substituted or unsubstituted hydrocarbon group, including a straight chain group or branched group.
  • the hydrocarbon group may contain at least one of a nitrogen atom, an oxygen atom, a phosphorous atom, a sulfur atom, and a halogen atom.
  • a ring containing an S atom it does not form an aromatic group.
  • a substitutent group of the hydrocarbon group may, for example, be an amino group, a guanidino group, a quaternary ammonium group, a hydroxyl group, a halogen compound, a carboxyl group, a carboxylate group, an amido group, a sulfinic acid group, a sulfonic acid group, a sulfate group, a phosphonic acid group, a phosphate group, a nitro group, and a cyano group.
  • Compound 3-2 is specifically preferred among the above exemplified compounds in view of realizing the purposes and effects of the present invention.
  • M represents a hydrogen atom, a metal atom or a quaternary ammonium group
  • Z represents a nitrogen-containing heterocyclic ring
  • n represents an integer of 0 to 5
  • R 9 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamido group, an arylcarbonamido group, an alkylsulfonamido group, an arylsulfonamido group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an aryls
  • Examples of metal atoms represented by M of Formula (4) include Li, Na, K, Mg, Ca, Zn, and Ag, and examples of quaternary ammonium include NH 4 , N(CH 3 ) 4 , N(C 4 H 9 ) 4 , N(CH 3 ) 3 C 12 H 25 , N (CH 3 ) 3 C 16 H 33 , and N (CH 3 ) 3 CH 2 C 6 H 5 .
  • Examples of the nitrogen-containing heterocyclic ring represented by Z of Formula (4) include a tetrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, an indole ring, an oxazole ring, a benzoxazole ring, a benzimidazole ring, a benzothiazole ring, a benzoselenazole ring and a naphthoxazole ring.
  • Examples of the halogen atom represented by R 9 of Formula (4) include a fluorine atom, a chlorine atom, a bromine atom and a iodine atom;
  • examples of the alkyl groups include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, an octyl group, a dodecyl group, a hydroxyethyl group, a methoxyethyl group, a trifluoromethyl group, and a benzyl group;
  • examples of the aryl group include a phenyl group and a naphthyl group;
  • examples of the alkylcarbonamido group include an acetylamino group, a pro
  • Exemplified Compounds 4-12 and 4-18 among the compounds exemplified as above, in view of satisfactorily realizing the objects and effects of the present invention.
  • Halogen atoms refer to any of the iodine, chloride, bromine, and fluorine atoms.
  • [X] / [Ag] is not less than 0.01
  • X - ⁇ X 2 occurs. This reaction becomes one of the factors in which X 2 easily undergoes cross oxidation with blackened silver to dissolve blackened silver, resulting in a decrease in memory capability. Consequently, it is preferable that the mol concentration of halogen atoms is as low as possible with respect to the mol concentration of silver. In the invention, 0 ⁇ [X] / [Ag] ⁇ 0.001 is more preferred.
  • the sum of mol concentration of each of the halogen species is [I] ⁇ [Br] ⁇ [Cl] ⁇ [F].
  • silver compounds such as silver iodide, silver chloride, silver bromide, silver oxide, silver sulfide, silver citrate, silver acetate, silver behenate, silver trifluoromethane sulfonate, silver p-toluenesulfonate, silver salts of mercapto compounds, and silver complexes of iminodiacetic acids.
  • silver salts compounds which do not contain halogen, carboxylic acid, nor a nitrogen atom exhibiting coordination capability with silver, and for example, preferred is silver p-toluenesulfonate.
  • the silver ion concentration in the electrolyte in the invention is preferably 0.2 mol/kg ⁇ [Ag] ⁇ 2.0 mol/kg.
  • the silver ion concentration is at most 0.2 mol/kg, a diluted silver solution is formed to lower the driving rate, while when it exceeds 2 mol/kg, solubility tends to lower to result in inconvenience of deposition during storage at low temperature.
  • the display element of the invention may optionally comprise various component layers besides the component elements described above.
  • the display element can comprise a porous scattering layer in enhancing display contrast or white display reflectance.
  • the porous white scattering layer applicable to the display element of the invention is formed by coating an aqueous mixture of an aqueous polymer substantially insoluble in an electrolyte solvent and a white pigment, and drying it.
  • White pigments applicable to the invention include, for example, titanium dioxide (anatase or rutile type), barium sulfate, calcium carbonate, aluminum oxide, zinc oxide, magnesium oxide and zinc hydroxide, magnesium hydroxide, magnesium phosphate, hydrogen magnesium phosphate, alkaline earth metal salt, talc, kaolin, zeolite, acid clay, glass; organic compounds such as polyethylene, polystyrene, acrylic resin, ionomer, ethylene-vinyl acetate copolymer resin, benzoguanamine resin, urea-formalin resin, melamine-formalin resin, polyamide resin. These are used singly or in combination, or in a state including voids changing refractive index.
  • Titanium dioxide, zinc oxide, zinc hydroxide are preferably employed among the white particles mentioned above in this invention.
  • employed as titanium oxide may be titanium oxide which has been subjected to a surface treatment employing an inorganic oxide (such as Al 2 O 3 , AlO(OH), or SiO 2 or titanium oxide which has been subjected to a treatment employing an organic compound such as trimethylolethane, triethanolamine acetic acid salts, or trimethylcyclosilane, in addition to the above surface treatment.
  • an inorganic oxide such as Al 2 O 3 , AlO(OH), or SiO 2
  • titanium oxide which has been subjected to a treatment employing an organic compound such as trimethylolethane, triethanolamine acetic acid salts, or trimethylcyclosilane, in addition to the above surface treatment.
  • titanium oxide or zinc oxide in preventing staining at high temperature and in reflectance due to index of refraction among these white particles.
  • aqueous polymer substantially insoluble in an electrolyte solvent a water-soluble polymer and a polymer dispersible in an aqueous solvent.
  • Examples of a water-soluble compound include proteins such as gelatin and its derivatives; natural compounds including polysaccharides, such as cellulose derivatives, starch, gum arabic, dextran, pullulan and carrageenan; and synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, a acrylamide polymer and their derivatives.
  • Gelatin derivatives include acetylated gelatin and phthalated gelatin
  • polyvinyl alcohol derivatives include an end alkyl-modified polyvinyl alcohol and an end mercapto-modified polyvinyl alcohol
  • cellulose derivatives include hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose.
  • gelatin and its derivatives are preferably used gelatin and its derivatives, and polyvinyl alcohol and its derivatives.
  • Examples of a polymer dispersible in an aqueous solvent include natural rubber latex and latexes of styrene butadiene rubber, butadiene rubber, nitrile rubber, chloroprene rubber and isoprene rubber; and thermosetting resins dispersible in an aqueous solvent, such as polyisocyanate, epoxy, acryl, silicone, polyurethane, urea, phenol, formaldehyde, epoxy-polyamide, melamine and alkyd resins and vinyl resin.
  • an aqueous polyurethane resin as described in JP-A 10-76621 , is preferred.
  • the expression, "being substantially insoluble in an electrolyte solvent” is defined as a dissolution amount per 1 kg of an electrolytic solvent being from 0 g to 10 g at a temperature of from -20 °C to 120 °C.
  • the dissolution amount can be determined by a weight measurement method or a component quantitative measurement method according to liquid chromatography or gas chromatography.
  • the aqueous mixture of an aqueous compound and a white pigment is preferably in the form of a white pigment dispersed in water according to a known dispersion method.
  • the volume ratio of aqueous compound/white pigment is preferably in the range from 1 to 0.01, and more preferably from 0.3 to 0.05.
  • the aqueous mixture of an aqueous compound and a white pigment is coated on a medium and may be coated at any position thereof, as long as it is on a constituting component between opposing electrodes of the display element but is provided preferably on the surface of at least one of the opposing electrodes.
  • Methods of providing on the medium include a coating system and a liquid-spraying system, including a spray system through gas phase, such as a system of jetting liquid droplets by employing vibration of a piezoelectric element, for example, a ink-jet head of a piezo-system, a bubble jet system (trade name) of jetting liquid droplets by using a thermal head employing bumping, and a spray system of spraying liquid by air pressure or liquid pressure.
  • a coating system can be chosen from commonly known coating systems, including, for example, an air doctor coater, a blade coater, a rod coater, a knife coater, a squeeze coater, a dipping coater, a reverse roller coater, a transfer roller coater, a curtain coater, a double roller coater, a slide hopper coater, a gravure coater, a kiss roller coater, a bead coater, a cast coater, a spray coater, a calender coater, and an extrusion coater.
  • an air doctor coater a blade coater, a rod coater, a knife coater, a squeeze coater, a dipping coater, a reverse roller coater, a transfer roller coater, a curtain coater, a double roller coater, a slide hopper coater, a gravure coater, a kiss roller coater, a bead coater, a cast coater, a spray coater, a calender coater,
  • An aqueous mixture of an aqueous compound and a white pigment which is provided on a medium may be dried by any method of evaporating water. Examples thereof include heating by a heat source, a heating method of using infrared light and a heating method employing electromagnetic induction. Distillation of water may be conducted under reduced pressure.
  • the expression "porous” is referred to as follows: the aqueous mixture of an aqueous compound and a white pigment is coated onto an electrode and dried to form a porous white scattering material.
  • An electrolyte solution containing silver or a compound containing silver in the molecule is provided on the material and sandwiched by opposing electrodes, and when an electric potential difference is applied between the opposing electrodes to cause a dissolution and deposition reaction of silver, ionic species are movable and penetrable between the electrodes.
  • the display element of the invention it is preferred to perform a hardening reaction of the aqueous compound by a hardening agent during or after coating or drying of the aqueous mixture.
  • hardening agent usable in the invention are cited hardening agents described in, for example, U.S. Patent No. 4,678,739 , col. 41; U.S. Patent No. 4,791,042 ; JP-A Nos. 59-116655 , 62-245261 , 61-18942 , 61-249054 , 61-245153 , and 4-218044 .
  • an aldehyde hardener an aziridine hardener, an epoxy hardener, a vinylsulfone hardener [e.g., N,N'-ethylene-bis(vinylsulfonylacetoamido)ethane], a N-methylol hardener [e.g., dimethylol urea], boric acid and a polymeric hardener (compounds described in JP-A 62-234157 ).
  • a vinylsulfone hardener or chlorotriazine hardener is preferably used singly or in combination.
  • polyvinyl alcohol it is preferable to employ boron-containing compounds such as boric acid and metaboric acid.
  • hardening agents are used preferably in amount of from 0.001 to 1 g per g of aqueous compound, and more preferably from 0.005 to 0.5 g. It is feasible to control humidity during heat treatment or hardening reaction to enhance layer strength.
  • the display element of the invention can contain a porous electrode containing a metal oxide.
  • metal oxides constituting the porous electrode in the invention include titanium oxide, silicon oxide, zinc oxide, tin oxide, Sn-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO) and aluminum-doped zinc oxide, and a mixture thereof.
  • the porous electrode can be formed, binding or contacting a plurality of particles of the metal oxide described above.
  • the average particle size of the metal oxide particles is preferably from 5 nm to 10 ⁇ m, and more preferably from 20 nm to 1 ⁇ m.
  • the specific surface area of the metal oxide particles is preferably from 1x10 -3 to 1x10 2 m 2 /g and more preferably from 1x10 -2 to 10 m 2 /g.
  • the metal oxide particles may be in any form, such as an amorphous form, needle form or a spherical form.
  • a sol-gel method or a sintering method can be employed as a method for forming or binding the metal oxide particles.
  • a sol-gel method or a sintering method examples thereof include, for instance, a method described in 1) Journal of the Ceramic Society of Japan 102, 2, p 200 (1994 ), 2) Yogyo-kyokai-shi 90 [4] p 157 , and 3) J. of Non-Cryst. Solids 82, 400 (1986 ).
  • a method for preparing a porous electrode which coats, on a substrate, a dispersion solution in which titanium oxide dendrimer particles prepared by a gas phase method are dispersed, followed by drying at 120 to around 150 °C to remove the solvent.
  • the metal oxide particles are preferably in the binding state, and it is preferred that such metal oxide particles have a durability of not less than 0.1 g, and preferably not less than 1 g, the durability measured according to a continuous weight load type surface meter (for example, a scratch meter).
  • porous in the invention refers to the state in which given potential difference between the opposed electrodes so as to cause dissolution and precipitation reaction of silver, ion species produced can move through the porous electrode provided.
  • the display element of the invention can comprise an electron insulation layer.
  • the electron insulation layer applicable to the invention may be a layer which has ion conductivity as well as electron insulation property.
  • Examples thereof include a solid electrolyte film made of a salt or a polymer having a polar group, a quasi-solid electrolyte film which is a porous film with high electron insulation property and has an electrolyte in the voids, a polymer porous film having voids and a porous film made of an inorganic material having low dielectric constant such as a silicon-containing compound.
  • Formation of a porous film can employ commonly known methods, including a sintering method (or a fusion method, in which polymer microparticles or inorganic particles are partially fused together with a binder and employing pores formed between particles), a subtraction method (in which a layer composed of a solvent-soluble organic or inorganic material and a solvent-insoluble binder is formed and the organic or inorganic material is dissolved by a solvent to form pores), a foaming method of allowing a polymeric material to foam by heating or degassing, a phase conversion method of allowing a mixture of polymers to be phase-separated by using a good solvent and a poor solvent, and a radiation exposure method of exposing to various kinds of radiations to form pores.
  • a sintering method or a fusion method, in which polymer microparticles or inorganic particles are partially fused together with a binder and employing pores formed between particles
  • a subtraction method in which a layer composed of a solvent-
  • JP-A Nos. 10-30181 and 2003-107626 JP-A No. 7-95403
  • Japanese Patent Nos. 2635715 , 2849523 , 2987474 , 3066426 , 3464513 , 3483644 , 3535942 and 3062203 JP-A Nos. 10-30181 and 2003-107626
  • JP-A No. 7-95403 JP-A No. 7-95403
  • Japanese Patent Nos. 2635715 , 2849523 , 2987474 , 3066426 , 3464513 , 3483644 , 3535942 and 3062203 Japanese Patent Nos. 2635715 , 2849523 , 2987474 , 3066426 , 3464513 , 3483644 , 3535942 and 3062203 .
  • the electrolyte may contain the following compounds when the electrolyte is liquid.
  • potassium compounds are KCl, KI, and KBr
  • lithium compounds are LiBF 4 , LiClO 4 , LiPF 6 , and LiCF 3 SO 3
  • tetraalkylammonium compounds are tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetraethylammonium borofluoride, tetrabutylammonium borofluoride, and tetrabutylammonium halide.
  • molten salt electrolytic composition described in Paragraphs [0062] - [0081] of JP-A 2003-187881 can be preferably used.
  • a compound can be employed, which becomes an oxidation-reduction pair such as I - /I 3 - , Br - /Br 3 - , or quinone/hydroquinone.
  • the electrolyte may contain the following compounds exhibiting electronic conductivity and ionic conductivity, when a supporting electrolyte is solid.
  • Such compounds include a vinyl fluoride polymer containing perfluorosulfonic acid, polythiophene, polyaniline, polypyrrole, triphenylamines, polyvinyl carbazoles, polymethylphenylsilanes, chalcogenides such as Cu 2 S, Ag 2 S, Cu 2 Se, or AgCrSe 2 , fluorine-containing compounds such as CaF 2 , PbF 2 , SrF 3 , LaF 3 , TlSn 2 F 5 , or CeF 3 , Li salts such as Li 2 SO 4 , Li 4 SiO 4 , or Li 3 PO 4 , ZrO 2 , CaO, Cd 2 O 3 , HfO 2 , Y 2 O 3 , Nb 2 O 5 , WO 3 , Bi 2 O 3 , AgBr, AgI, CuCl, CuBr, CuBr, CuI, LiI, LiBr, LiCl, LiAlCl 4 , LiAlF 4
  • a thickener to the electrolyte in the display element of the invention.
  • examples thereof include gelatin, gum Arabic, poly(vinyl alcohol), hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, poly(vinylpyrrolidone), poly(alkylene glycol), casein, starch, poly(acrylic acid), poly(methylmethacrylic acid), poly(vinyl chloride), poly(methacrylic acid), copoly(styrene-maleic anhydride), copoly(styrene-acrylonitrile), copoly(styrene-butadiene), poly(vinyl acetals), such as poly(vinyl formal and poly(vinyl butyral), poly(esters), poly(urethanes), phenoxy resins, poly(vinylidene chloride), poly(epoxides), poly(carbonates), poly(vinyl acetate), cellulose esters,
  • thickeners may be employed in combinations of at least two types. Further listed may be the compounds described on pages 71 - 75 of JP-A S64-13546 . Of these, polyvinyl alcohols, polyvinylpyrrolidones, hydroxypropyl celluloses, and polyalkylene glycols are preferably employed in view of enhancement of compatibility with various additives and improvement of white particle dispersion stability.
  • the component layers of the display element of the invention may include subsidiary layers such as a protective layer, a filter layer, an antihalation layer, a cross-over light cutting layer, or a backing layer.
  • subsidiary layers such as a protective layer, a filter layer, an antihalation layer, a cross-over light cutting layer, or a backing layer.
  • a component layer between the opposing electrodes of the display element of the invention will further be explained.
  • a component layer containing a positive hole transporting material as the component layer regarding the display element of the invention.
  • the positive hole transporting material include aromatic amines, triphenylene derivatives, oligothiophene compounds, polypyrroles, polyacetylene derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polythiophene derivatives, polyaniline derivatives, polytoluidine derivatives, CuI, CuSCN, CuInSe 2 , Cu(In,Ga)Se, CuGaSe 2 , Cu 2 O, CuS, CuGaS 2 , CuInS 2 , CuAlSe 2 , GaP, NiO, CoO, FeO, Bi 2 O 3 , MoO 2 , and Cr 2 O 3 .
  • the substrate usable in the invention are preferably used synthetic plastic films composed, for example, of polyolefins such as polyethylene or polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylenedinaphthalene dicarboxylate, polyethylene naphthalates, polyvinyl chloride, polyimide, polyvinyl acetals, or polystyrene.
  • polyolefins such as polyethylene or polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylenedinaphthalene dicarboxylate, polyethylene naphthalates, polyvinyl chloride, polyimide, polyvinyl acetals, or polystyrene.
  • syndiotactic-structured polystyrenes These can be prepared, employing the methods described, for example, in JP-A 62-117708 , JP-A 1-46912 , and JP-A 1-178505 .
  • metal substrates of stainless steel paper supports such as baryta paper or resin-coated paper, supports composed of the above plastic film having thereon a reflection layer, and those described, as a support, in JP-A 62-253195 (pages 29 - 31). It is possible to preferably employ those described on page 28 of RD No. 17643, from the light column on page 647 to the left column on page 648 of RD No. 18716, and on page 879 of RD No. 307105. As described in U.S. Patent No. 4,141,735 , the supports can be used which is subjected to a thermal treatment at a temperature below Tg so that core-set curl is minimized.
  • the surface of these supports may be subjected to a surface treatment for the purpose of enhancement of adhesion of the support to another constitution layer.
  • a surface treatment may be a glow discharge treatment, an ultraviolet radiation treatment, a corona treatment, and a flame treatment.
  • employed may be supports described on pages 44 - 149 of Kochi Gijutsu (Known Technology) No.5 (published by AZTEC Japan., March 22, 1991 ). Further listed are those described on page 1009 of RD No. 308119, as well as in the item "Supports" on page 108 of Product Licensing Index Volume 92.
  • employed may be glass substrates and epoxy resins kneaded with glass powder.
  • At least one of the opposing electrodes is a metal electrode in the display element of the invention.
  • the metal electrode may be metals such as platinum, gold, silver, copper, aluminum, zinc, nickel, titanium or bismuth, as well as alloys thereof, which are known in the art.
  • Preferred metals employed in the metal electrodes are those which exhibit a work function near the oxidation-reduction potential of silver in the electrolyte.
  • a silver electrode or an electrode composed of silver in an amount of at least 80% is advantageous to maintain reduction condition of silver, and further, results in anti-staining of electrodes.
  • Employed as a method to prepare the electrodes may be conventional ones such as an evaporation method, a printing method, an ink-jet printing method, a spin coating method, or a CVD method.
  • Transparent electrodes are not particularly limited as long as they are transparent and electrically conductive. Examples thereof include indium tin oxide (ITO), indium zinc oxide (IZO), fluorine-doped tin oxide (FTO), indium oxide, zinc oxide, platinum, gold, silver, rhodium, copper, chromium, carbon, aluminum, silicon, amorphous silicon, and BSO (bismuth silicon oxide).
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • FTO fluorine-doped tin oxide
  • an ITO layer may be subjected to mask evaporation on a substrate employing a sputtering method, or after forming an ITO layer on the entire surface, patterning may be performed employing photolithography.
  • the surface resistance value is preferably at most 100 ⁇ / ⁇ , but is more preferably at most 10 ⁇ / ⁇ .
  • the thickness of the transparent electrode is not particularly limited, but is commonly 0.1 to 20 ⁇ m.
  • Sealing agents may be employed in the display element of the invention, if desired.
  • Sealing agents are those which perform sealing so that leak to the exterior is minimized, and are called sealants.
  • Employed as sealing agents may be heat curing, light curing, moisture curing, or anaerobic curing type resins such as epoxy resins, urethane resins, acryl resins, vinyl acetate resins, en-thiol resins, silicon-containing resins or modified polymer resins.
  • the columnar materials provide a strong self-supporting capability (strength) between substrates.
  • listed may be a cylindrical form, a quadrangular form, an elliptic from, and a trapezoidal form which are arranged at definite intervals in a specified pattern such as a lattice. Further employed may be stripe-shaped ones arranged at definite intervals. It is preferred that the columnar materials are not randomly arranged but arranged at an equal distance so that the interval gradually varies, or a predetermined pattern is repeated at a definite cycle so that the distance between substrates is nearly maintained and image display is not degraded. When the columnar materials are such that the ratio of the area occupied by the display region of a display element is 1 - 40%, sufficient strength as a display element for commercial viability is obtained.
  • Spacers may be provided between paired substrates in order to maintain a uniform gap between them.
  • spacers exemplified may be spheres composed of resins or inorganic oxides. Further suitably employed are adhesion spacers, the surface of which is coated with thermoplastic resins.
  • Columnar materials only may be provided in order to maintain a uniform gap between the substrates. However, both spacers and columnar materials may be provided. Instead of the columnar materials, only spacers may be employed as space-maintaining members.
  • the diameter of spacers when a columnar material is formed, is at most its height, but is preferably equal to the above height. When no columnar material is formed, the diameter of spacers corresponds to the thickness of the cell gap.
  • sealing agents columnar materials, and electrode patterns, employing a screen printing method in the present invention.
  • screen printing methods a screen, on which predetermined patterns are formed, is applied onto the electrode surface, and printing materials (compositions to form columnar materials such as light-curing resins) are placed on the screen. Subsequently, a squeegee is moved at a predetermined pressure, angle and rate. By such action, the printing materials are transferred onto the above substrate via the pattern of the screen. Subsequently, the transferred materials are thermally cured and dried.
  • resinous materials are not limited to light-curing resins, but also employed, for example, may be heat curable resins such as epoxy resins or acryl resins, as well as thermoplastic resins.
  • thermoplastic resins are: polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polymethacrylic acid ester resins, polyacrylic acid ester resins, polystyrene resins, polyamide resins, polyethylene resins, polypropylene resins, fluororesins, polyurethane resins, polyacrylonitrile resins, polyvinyl ether resins, polyvinyl ketone resins, polyether resins, polyvinylpyrrolidone resins, saturated polyester resins, polycarbonate resins, and chlorinated polyether resins. It is preferable that resinous materials are employed in the form of a paste, while dissolved in suitable solvents.
  • a spacer is provided on at least one side of the substrate, and paired substrates are placed so that the electrode forming surfaces face each other, whereby a vacant cell is formed.
  • paired substrates are placed so that the electrode forming surfaces face each other, whereby a vacant cell is formed.
  • Preparation of a display element may be achieved by injecting an electrolyte composition between the substrates, employing a vacuum injection method.
  • an electrolyte composition may be dripped onto the surface of one of the substrates and then a liquid crystal composition is injected simultaneously sealed when the substrates are adhered to each other.
  • the display element of the present invention undergoes an electrode reaction of an electrode with silver in the electrolyte. Consequently, it easy to understand the presence of overvoltage during silver dissolution and deposition. Since the magnitude of overvoltage is controlled by exchange current density, it is assumed that the fact that as shown in the present invention, after formation of blackened silver, deposition of blackened silver continues via application of voltage lower than the deposition overvoltage, is that the surface of the blackened silver results in less excessive electric energy, whereby it is possible to easily perform electron injection.
  • Driving operation of the display element of the invention may be simple matrix driving or active matrix driving.
  • Simple matrix driving refers to the driving method in which electric current is sequentially applied to a circuit in which a positive electrode line containing a plurality of positive electrodes faces a negative electrode line containing a plurality of negative electrodes so that each line intersects in the perpendicular direction.
  • simple matrix driving it is possible to simplify the circuit structure and the driving IC, resulting in advantages such as lower production cost.
  • Active matrix driving refers to a system in which scanning lines, data lines, and current feeding lines are formed in a checkered pattern and driving is performed by TFT circuits arranged in each of the squares of the checkered pattern. Since it is possible to switch for each pixel, advantages result in gradation as well as memory function. For example, it is possible to employ the circuit described in Fig. 5 of JP-A 2004-29327 .
  • the display element of the invention can be applied to electronic book related fields, ID card related fields, public information related fields, transportation related fields, broadcasting related fields, account settling fields, and distribution and logistics related fields.
  • Typical examples of the products applied include door keys, student identification cards, employee ID cards, various club membership cards, convenience store cards, department store cards, vending machine cards, gas station cards, subway and railroad cards, bus cards, cash cards, credit cards, highway cards, driver licenses, hospital medical examination cards, health insurance cards, Basic Resident Registers, passports, and electronic books.
  • Electrolytic Solution 1 Sodium iodide of 90 mg and 75 mg of silver iodide were added to 2.5 g of dimethyl sulfoxide, and allowed to completely dissolve. Thereafter, 150 mg of polyvinylpyrrolidone (with an average molecular weight of 15,000) were added to the solution and stirred over one hour while heated at 120°C, whereby Electrolytic Solution 1 was prepared.
  • An ITO film at a pitch of 145 ⁇ m and an electrode width of 130 ⁇ m, was formed on a 1.5 mm thick 2 cm x 4 cm glass substrate employing a conventional method, whereby a transparent electrode (namely Electrode 1) was prepared.
  • a silver-palladium electrode (namely Electrode 2) with a thickness of 0.8 ⁇ m, a pitch of 145 ⁇ m and an electrode gap of 130 ⁇ m was prepared on a 1.5 mm thick 2 cm x 4 cm glass substrate employing a conventional method.
  • a mixed dispersion which was obtained by mixing a 2% isopropanol solution of polyvinyl alcohol (with an average polymerization degree of 3500 and a saponification degree of 87%) and titanium oxide in an amount of 20% by weight, and dispersing the mixture in an ultrasonic disperser, was coated at 100 ⁇ m on Electrode 2 whose peripheral portion was hemmed by an olefin type sealing agent containing spherical glass beads of an average particle diameter of 40 ⁇ m at a volume ratio of 10%, dried at 15°C for 30 minutes, and further dried at 45 °C for one hour, whereby Electrode 3 was obtained.
  • Electrode 3 was superposed on Electrode 1, followed by heating and pressing, whereby an empty cell was prepared.
  • Electrolytic Solution 1 was injected into the empty cell via a vacuum injection method and the inlet for injection was sealed with epoxy type ultraviolet ray-curable resin, whereby Display Element 1 was prepared.
  • Display Element 2 was prepared in the same manner as in Display Element 1, except that the following electrode 4 was used instead of electrode 1.
  • Electrode 4 An aqueous 4% by weight gelation solution, in which dyes AI-1, AI-2 and AI-3 described below were dissolved, was coated at a thickness of 25 ⁇ m on the surface of the glass substrate of Electrode 1 opposite the transparent electrode, gelatin-set at 5°C, and dried at 45°C for one hour, whereby Electrode 4 was obtained.
  • L* value, a* value and b* value of Display Element 1 were measured at a D65 light source, employing a spectro-colorimeter CM-3700d, produced by Konica Minolta Sensing, Inc., and was defined as L1, a1 and b1, respectively.
  • L* value, a* value and b* value of news papers available on the market were measured, and was defined as L2, a2 and b2, respectively.
  • ⁇ E was determined from the following formula for evaluation of color tone difference.
  • ⁇ E 1 [ L ⁇ 2 - L ⁇ 1 2 + a ⁇ 2 - a ⁇ 1 2 + b ⁇ 2 - b ⁇ 1 2 1 / 2
  • Display Elements 3 through 10 were prepared in the same manner as in Display Element 1, except that the coating amount of titanium oxide of Electrode 3 varied to give a reflectance of 70%, 65%, 60%, 55%, 50%, 45%, 40% and 35%, respectively, the reflectance being measured employing a 550 nm light of CM-3700d.
  • Display Elements 11 through 18 were prepared in the same manner as in Display Elements 3 through 10, respectively, except that Electrode 1 was replaced with the following Electrode 5.
  • Electrode 5 was prepared in the same manner as in electrode 4, except that the following optical brightening agent W-1 (at a coating amount of 200 mg/m 2 ) was used instead of the dyes.
  • Display Element 19 was prepared in the same manner as in Display Element 14 of Example 2, except that optical whitening agent W-1 was removed from Electrode 5, and added to the Electrolytic Solution 1.
  • Display Element 20 was prepared in the same manner as in Display Element 14 of Example 2, except that the dimethylsulfoxide was replaced with dimethylformamide of the same amount, the silver iodide was replaced with silver chloride of the same mol, and the sodium iodide was replaced with Exemplified compound (4-12) of the same mol.
  • Display Element 21 was prepared in the same manner as in Display Element 20 above, except that Optical brightening agent W-1 was removed from Electrode 5, and added to Electrolytic Solution 1.
  • Display Element 22 was prepared in the same manner as in Display Element 14 of Example 2, except that the dimethylsulfoxide was replaced with propylene carbonate of the same amount, the silver iodide with silver chloride of the same mol, and the sodium iodide with Exemplified compound (4-12) of the same mol.
  • Display Element 23 was prepared in the same manner as in Display Element 22 above, except that Optical brightening agent W-1 was removed from Electrode 5, and added to Electrolytic Solution 1.
  • Display Element 24 was prepared in the same manner as in Display Element 14 of Example 2, except that the dimethylsulfoxide was replaced with propylene carbonate of the same amount, the silver iodide with silver p-toluene sulfonate of the same mol, and the sodium iodide with Exemplified compound (4-12) of the same mol.
  • Display Element 25 was prepared in the same manner as in Display Element 24 above, except that Optical brightening agent W-1 was removed from Electrode 5, and added to Electrolytic Solution 1.
  • Display Element 26 was prepared in the same manner as in Display Element 24 above, except that Exemplified compound (4-12) was replaced with Exemplified compound (3-4) of 0.7 times by mole the amount Exemplified compound (4-12).
  • Display Element 27 was prepared in the same manner as in Display Element 25 above, except that Exemplified compound (4-12) was replaced with Exemplified compound (3-4) of 0.7 times by mole the amount Exemplified compound (4-12).
  • a driving condition giving an *L value of 65 was determined, measured employing a D65 light source of a spectro-colorimeter CM-3700d produced by Konica Minolta Sensing Inc. Subsequently, when each display element above was driven under the driving condition to exhibit white, an *L value, an *a value and a *b value were determined, and designated as L3, a3 and b3, respectively. Further, after the element was allowed to stand at 65°C for two weeks, an *L value, an *a value and a *b value were determined in the same manner as above, and designated as L4, a4 and b4, respectively.
  • ⁇ E 2 L ⁇ 4 - L ⁇ 3 2 + a ⁇ 4 - a ⁇ 3 2 + b ⁇ 4 - b ⁇ 3 2 1 / 2
  • inventive display elements having a constitution defined in the invention excel in white display stability even after storage at high temperature for a long term.

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